Sensitized photographic material



Feb. 8, 1944. J KENDALL 2,340,882

SENS ITIZED PHOTOGRAPHIC MATERIALS Original Filed Aug. 8, 1936 2 Sheets-Shet 1 W1 l/A/SE/VS/T/ZED CONTROL EMULSION W2 EMULS/ON CONTA/N/NG DY 0FXAMPL 54 W 3 EMULSIOA COA/TA/N/NG DYE 0FXAMPL 55 W 4 EMULS/ON CO/WA/N/NG DYE 0F EXAMPLE 56 W5 EMULS/O/V CONTA/N/NG DYE 0F EXAMPLE 57 cl0/llt DaVldKZlZdClZZ INVENTOR.

A TT ORNE Y Feb. 8, 1944. J D, KENDALL 2,340,882

SENSITIZED PHOTOGRAPHIC MATERIALS Original Filed Aug. 8, 1956 2 Sheets-Sheet 2 W 7 A-MULS/O/V CONTA/N/NG DYE 0FXAMPL 39 W 6 MOL s/o/v CONTA/N/NG DYE OFEXAMPLE 40 W .9 fMl/LS/O/V CONTAIN/N6 DYE 0F EXAMPLE 4/ W0 EMULS/ON CONT A/N/NG DYE 0/ EXAMPLE 45 /Mlt DGVZ CZ [(Ellddll INVENTOR.

A T TORNEY Patented Feb. 8, 1.944

2,340,882 SENSITIZED PHOTOGBAPHIC MATERIAL John David Kendall, Iiford, England, assifllor to Iliord Limited, Iliord, England, a British com- Original application August 8, 1936, Serial No.

Divided and this application August 115, 1941, Serial No. 407,054. In Great Britain August 16, 1935 12 Claims. (Ci. 957) This invention relates to the production of dyestufls.

It is an object of this invention to produce compounds comprising two heterocyclic nitrogen nuclei linked by a chain of atoms including one or more nitrogen atoms. According to the present invention a process for the production of compounds of the above type comprises condensing a quaternary salt of a heterocyclic nitrogen compound containing a reactive thioether or selenoether group in the on or 7 position to the nitrogen atom with ammonia or an amidine or the salt of one of these compounds.

The heterocyclic nitrogen compound whose quaternary salt is to be employed may consist of any one 01. the well-known heterocyclic nitrogen compounds such as substituted and unsubstituted thiazoles, thiazolines, oxazoles, oxazolines, selenazoles, selenazolines, pyridines, quinolines, indolenines, diazines, e. g., pyrimidines, thiodiazoles and qulnazolines, and the corresponding polycyclic compounds such as benzthiazoles, naphthathiazole and anthrathiazole. The compound employed may be the quaternary salt of the thioether or selenoether derivative of the heterocyclic nitrogen compound, or it may be the salt obtained from the corresponding thione or selenone.

Whilst ammonia and the amidine may be employed as such, generally it is found more convenient to employ salts of these compounds, such as ammonium nitrate and acetamidine hydrochloride and to carry out the reaction in the presence of an acid binding agent; thus the reaction may be carried out in the presence of a solvent such as pyridine which also acts as an acid binding agent, or a neutral solvent such as alcohol may be employed together with a strong acid binding agent such as sodium ethoxide.

Further specific examples of the nitrogen compounds which may be employed are amidines such as formamidine, acetamidine, benzamidine, guanidine, urea, thiourea and O-alkyl pseudo ureas and S-alkyl pseudo thioureas.

The ammonia and amidine compounds which may be employed in accordance with the present invention may be expressed by one of the following general formulae:

in which X represents any monovalent substituent, such as hydrogen, an alkyl, aryl or aralkyl group or a hydroxy, alkoxy, thiol, thioether, amino or substituted amino group. It will be observed that these compounds have replaceable leaving the nitrogeneous residue as the link between the heterocyclic nitrogen nuclei; thus it is believed that the reaction of the present invention may be illustrated by the following equations:

In the case of those amidines which readily break up to give ammonia it is believed that the reaction may fol1ow the mechanism of the first equation to give a compound in which the linking chain consists only of a single nitrogen atom.

According to a modification of the process oi the present invention, dyestuffs are obtained by condensing a quaternary salt of a heterocyclic nitrogen compound having a reactive thio-ether or seleno-ether group or a reactive amino-vinyl, acyl-amino-vinyl, aryl-amino-vinyl, or acylaryl-amino-vinyl grouping in the a or '7 position to a nitrogen atom with an organic compound containing two amino groups linked by a single bond or by a conjugate chain of carbon atoms some or all of which form part of one or more aromatic carbo-cyclic rings, and which may be represented by the general formula where n is 0 or a positive integer, or salts of such compounds. I

Examples of such compounds are:

hydrazine H2NNH2 the oand p-arylene diamine such as oand p-phenylenediamines benzidine and its homologues such as dianisidine and 4:4- diamino-stllbenes, e. g.

The reaction may be carried out in the presence of a solvent with or without an acid binding agent. When an acid binding agent is required, e. g. when using salts of these compounds, the reaction may be carried out in a neutral solvent such as alcohol together with an acid binding agent such as sodium ethoxide or sodium acetate, or it may be carried out in the presence of a basic solvent such as pyridine which acts the acid binding agent.

The quaternary salts of the same heterocyclic nitrogen compounds may be be employed in this modified process as in the process already described.

The. hydrazine and other compounds are sim lar to ammonia and the amidines in having replaceable hydrogen atoms attached to the nitrogen atoms and it is believed that the mechanism of the reaction is similar in consequence and possibly may be illustrated by the following equations:

+ BK ZCoHANHCOCHl Many of the products of the present invention are coloured and are sensitisers for photographic silver halide emulsions. The dyestuffs obtained by the reaction of quaternary salts or heterocyclic nitrogen compounds having reactive aminovinyl or substituted aminovinyl groups with organic compounds such as hydrazine which may be represented by the formula ver where n is 0 or a positive integer are particularly good sensitisers, and the present invention includes a photographic silver halide emulsion sensitised with such a dyestufl.

One or more of the dyestuffs may be incorporated in the photographic silver halide emulsion before it is coated on a support, or alternatively the support (e. g. a film or plate) coated with the emulsion may be bathed in a solution of one or more of the dyestuffs. The actual quantity incorporated may vary to a certain extent with the individual dyestuif and with the ultimate effect which it is desired to obtain, as an indication, however, of the order of the quantities which may be employed, cos. of a one in one thousand solution of the dyestufl may be incorporated in six and a half litres of emulsion equivalent to about 250 grams of silver nitrate, or the coated support may be bathed in a one in one thousand solution of the dyestuff; the strength of the solution may vary according to the dyestuff used and may be as low as one in ten thousand.

The process of the present invention is illustrated by the following specific examples, several of which give an indication of the sensitising action of the products.

Example 1 2.23 grams of 1:3:3-trimethyl-2-w-acetanilidovinyl-indolenimn iodide and 1.05 gms. of hydrazine hydrochloride were mixed with 20 cos. of pyridine and the whole warmed on a water bath for about half an hour when an orange dye formed. The mixture was then gently boiled under a reflux condenser for about twenty minutes. The liquid obtained was then poured into aqueous potassium iodide solution when the dyestufi was precipitated out as a crimson solid and recrystallized from methyl alcohol to give a dye which decomposed at about 250 C. This dye is a very powerful senstiser for silver chloride emulsions and extends their sensitivity ranges to about 5900 A. with a fiat sensitising curve over the range from about 4600 A. to about 5400 A. This dyestuil' is a mono hydriodide salt of the dye base of the formula:

CH: CH3 CH3 CH1 Example 2 22.3 grams of 1:3:3-trimethyl-2-w-acetanilidovinyl indelenium iodide and 9.05 grams of pphenylenediamine hydrochloride and 200 cos. of pyridine were mixed and heated together on a water bath for twenty-five minutes and then gently boiled under a reflux condenser for a further ten minutes. The orange solution obtained was then poured into water when small brickred crystals quickly settled out. 'Ihese were filtered ofi', washed with spirit and ether-and dried and melted at 272 C. This dyestufi is a dihydriodide salt of the dye base of the formula:

Example 3 11.2 grams of 1-w-acetanilido-vinyl-benzthiazole ethiodide, 4.5 grams 01' p-phenylenediamine hydrochloride were mixed together with 300 cos. of pyridine. The solids dissolved up and the solution became yellow in colour. The solution was then heated on a water bath for forty minutes, after which it was gently boiled under a reflux condenser for ten minutes, when a crimson solid separated out. The mixture was then poured into water and the crimson crystals which separated out were filtered ofi', washed and dried. They melted at 285 C. This dyestuil' is a dihydriodide salt of the dye base of the formula:

Example 4 21 grams of 1 -w-acetanilido-vinyl-benzoxazole methiodide and 9.05 grams of paraphen'ylenediamine hydrochloride were mixed with 100 ccs. of pyridine and gently boiled together. A deep yellow solution was obtained and orange coloured crystals were deposited from the hot solution. After allowing this solution to stand until cool the crystals were filtered oil, washed and dried. They had a melting point higher than 305 C. This dyestufi is a di-hydriodide salt the dye base of the formula:

f CH; CH;

Example 5 trample 6 22.3 gramsoi 1:3:3-trimethyl-2-u-acetanilido- Ivinyl-indolenium iodide, 9.2 grams or benzidine and 150 cos. of dry spirit were gently boiled toaether under a refiux condenser for 30 minutes. The substances dissolved in the spirit and then orange crystals with a bluish reflex separated from the hot solution. After cooling the solid was filtered of! from the liquors and well washed $311 pirit and ether. The crystals melted above A further experiment showed that this reaction could be carried out equally well using Pyridine in place of the alcohol. This dyestufi is a dillydriodide salt of the dye base or the formula:

Example 7 22.5 grams 0! l-w-acetanilido-vinyl-benzthiazole ethiodide and 9.2 grams of benzidine were mixed together with 200 ccs. of dry spirit and 'the whole gently boiled for 30 minutes. A brown crystalline solid separated out, which was filtered off, washed and dried and obtained as dark brown crystals melting at 260 C. This dyestufi! is a dihydriodide salt of the dye base of the formula:

Example 8 21 grams of 1-w-acetanilido-vinyl-benzoxazole methiodide and 9.2 grams of benzidine were mixed together with cc of alcohol and the whole gently heated for a ew minutes. An intense yellow solution was obtained from which small'orange crystals separated out. These were filtered of! and washed and dried and obtained as orange yellow powder having a melting point above 300 C. This dyestuff is a di-hydriodide salt of the dye base of the formula:

Example 9 18.1 grams of l-methylthiol benzthiazole were heated together with 18.6 grams of methyl-ptoluene sulphonate for three and a half hours at -140 C. 18.4 grams of benzidine and 200 ccs. of spirit were added and the mixture was gently warmed for twenty minutes when a light yellow solid was deposited and mercaptan evolved. The solid was filtered oil, well washed with benzene spirit and ether and obtained as almost colourless powder melting above 300 C.

Example 10 22.3 grams of 1:3:3-trimethyl-2-w-acetanilidovinyl indolenium iodide, 12.2 grams of di-anisidine (2:2'-dimethoxy benz idine) and 100 ccs. of pyridine were mixed together and gently boiled under a reflux condenser for thirty minutes. A tive integer not greater than 2, and'the acid salts deep orange solutionwas obtained from which a of such =dyestuifs wherein a salt group is atbrick red solid was deposited on cooling. This tached to a nitrogen atom rendering such atom solid was filtered on, well washed and obtained pentavalent.

a small brick red. crystals, melting at 282 C. a 6. Aphotographic emulsion containing an acid with decomposition. 'Ihis dyestuif-is a di-hydriosalt of a dyestuif of the general formula and havdide salt .of the dye base of the formula: ing the characteristics of the dyestui'f set forth H CH OH in claim c 3 0 0cm 'l. A photographic emulsion containing a dyecm mm of the general formula:

O=CH-CH=N-C O =cn-on=c I] D (1,

N (am r N (6n=cH):, c=cn-cn=n-u=cn-cn=c icn=cm N EH4 1'1 I This application is a division of applicant's copending application Serial No. 95,033, filed August 8. 1936, now U. 8. Patent 2,307,049.

wherein D and D1 are the residues of heterocyclic nitrogen compounds of the type used in cyanine dyes, R and R1 are alkyl groups and p is a posi- Inthe comm drawings the sensitivity tive integer not greater than 2, and the acid salts curves of Figures 1-10 are those of an unsensitized control emulsion and an emulsion containa:2 :3 gg gg gg z gg g m ggg gg t gzg fi ing the dyes of Examples 1 to 8, inclusive, and l0,

- valent. g fgh 8. A photographic emulsion containing an acid salt of a dyestufl of the general formula and l. A phm containing dye having the characteristics of the dyestul! set stuff of the general formula. forth in claim 7 x d 9. Asilver halide emulsion comprising a dye N \(CH=CH)IFC=CH'CH=N A)I-IN=CHCH=C (CH=CH)7-;N corresponding with the formula: v

R R1 wherein Dand D are the residues of heterocyclic nitrogen compounds of the type used in cyanine dyes, R and R1 are alkyl groups. D 18 a positive ;1;: 311- :1 c3:011- integer not greater than 2, q is a positive in- N teger not greater than 2 and A is a chain of u -an even number of carbon atoms not exceeding 10 alternately doubly and singly bonded. the carin which Y and Z stand for a member selected bon atoms of A directly linked to the nitrogen from t group gonsistmg of 5 5 atoms each forming with the'next adjacent carand bon atom in the chain part of a carbocyclic nu- 40 R cleus, and the acid salts of such dyestuffs wherein a salt group is attached to a nitrogen atom rendering such atom pentavalent. R,

2. A photographic emulsion containing an acid salt of a dyestuif of the general formula and havwherein R1 and R: stand for alkyl groups, R ing the characteristics of the dyestuil set forth stands for alkyl, Ar stands for an aromatic radiin claim 1. cal which contains at least one benzene nucleus 3. A photographic emulsion containing a dyebut no more than two benzene nuclei, X stands stud of the general'formula: for an anion capable of precipitating the dye.

n p -u r 1;I-(CH=CH),-z C=OHCH=N-() N=CH-CH=C(CH=CH)p-I'N Bi g-l I whereinD and D1 are the residues of heterocyclic 10. A silver halide emulsion compri in a y nitrogen oompoimds of the type used in cyanine c rresp ndin wi h the f rmula:

dyes, R and R1 are alkyl groups, p is a positive R integer not greater than 2, and q is a positive integer, and the acid salts of such dyestufls wherein a salt group is attached to a nitrogen atom so rendering such atom pentavalent.

4. A photographic emulsion containing an acid N salt of a dyestuii of the general formula and I having the characteristics of the dyestufl set forth R X in claim 3. where R1 and R: stand for alkyl groups. R stands 5; A photographic emulsion containing a dyefor alkyl, Ar stands for an aromatic radical which stuff of the general formula: contains at least'one benzene nucleus but no D D1 w"- un-(cn=cn ,-.,-c=cn-cH=NOcn=cn N=CH-CH=C(CH=CH),-|-II-I R where D and D1 are the residues of heterocyclic more than two benzene nuclei, x stands for an nitrogen compounds of the type used in cyanine anion capable of precipitating the dye. dyes, R and R1 are alkyl groups and p is a posi- 11. A light sensitive silver halide emulsion contaming a small amount or a. mono-hydrlodide salt or the dye base of the formula:

cm om cm on;

c=cn-cn=N--N=cn-ca=c p (2H1 (EB:

12. light sensitive silver halide emulsion contaming a small amount of a di-hydriodide salt or the dye base 01 the formula:

CH: CH: CH: /CH| H1 JOHN DAVID KENDAIL.

Certificate of Correction Patent No. 2,340,882. February 8, 1944.

JOHN DAVID KENDALL It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows: Page 2, first column, line 25, after the Word acts insert as; page 4, first column, line 14, for that portion of the formulareading CH read 0H,; and second column, 'line 31, claim 9, in the formula, for

Y read I N N R/ \X R/ \X and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 25th day of April, A. D. 1944.

[SEAL] LESLIE FRAZER,

Acting Commissioner of Patents. 

